EP3014652B1 - Système de couches pour cellules solaires à couches minces avec couche-tampon en sulfure de sodium - Google Patents
Système de couches pour cellules solaires à couches minces avec couche-tampon en sulfure de sodium Download PDFInfo
- Publication number
- EP3014652B1 EP3014652B1 EP14734459.2A EP14734459A EP3014652B1 EP 3014652 B1 EP3014652 B1 EP 3014652B1 EP 14734459 A EP14734459 A EP 14734459A EP 3014652 B1 EP3014652 B1 EP 3014652B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- buffer layer
- sodium
- sulfide
- absorber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000872 buffer Substances 0.000 title claims description 143
- 239000010409 thin film Substances 0.000 title claims description 43
- AXCIGYOXXCQVPM-UHFFFAOYSA-N [In]=S.[Na] Chemical compound [In]=S.[Na] AXCIGYOXXCQVPM-UHFFFAOYSA-N 0.000 title description 22
- 239000011248 coating agent Substances 0.000 title description 5
- 238000000576 coating method Methods 0.000 title description 5
- 239000011734 sodium Substances 0.000 claims description 97
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 60
- 229910052708 sodium Inorganic materials 0.000 claims description 60
- 239000006096 absorbing agent Substances 0.000 claims description 54
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical group [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 35
- 239000010949 copper Substances 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 29
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 23
- 229910052738 indium Inorganic materials 0.000 claims description 19
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 238000000231 atomic layer deposition Methods 0.000 claims description 8
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000005240 physical vapour deposition Methods 0.000 claims description 6
- -1 chalcopyrite compound Chemical class 0.000 claims description 5
- 238000000224 chemical solution deposition Methods 0.000 claims description 5
- 238000002207 thermal evaporation Methods 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000005118 spray pyrolysis Methods 0.000 claims description 4
- 238000005566 electron beam evaporation Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 description 23
- 229910052711 selenium Inorganic materials 0.000 description 20
- 239000011669 selenium Substances 0.000 description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 18
- 230000008569 process Effects 0.000 description 17
- 239000011593 sulfur Substances 0.000 description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 14
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- RLIUKKHIBMHFOK-UHFFFAOYSA-N indium sodium Chemical compound [Na].[In] RLIUKKHIBMHFOK-UHFFFAOYSA-N 0.000 description 3
- SIXIBASSFIFHDK-UHFFFAOYSA-N indium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[In+3].[In+3] SIXIBASSFIFHDK-UHFFFAOYSA-N 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000528 Na alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052798 chalcogen Inorganic materials 0.000 description 2
- 150000001787 chalcogens Chemical class 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000002329 Inga feuillei Species 0.000 description 1
- BKQMNPVDJIHLPD-UHFFFAOYSA-N OS(=O)(=O)[Se]S(O)(=O)=O Chemical compound OS(=O)(=O)[Se]S(O)(=O)=O BKQMNPVDJIHLPD-UHFFFAOYSA-N 0.000 description 1
- QEWCDOSBINPOPV-UHFFFAOYSA-N S(=O)(=O)(O)[Se]S(=O)(=O)O.[Sn].[Zn].[Cu] Chemical compound S(=O)(=O)(O)[Se]S(=O)(=O)O.[Sn].[Zn].[Cu] QEWCDOSBINPOPV-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003363 ZnMgO Inorganic materials 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011364 vaporized material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02425—Conductive materials, e.g. metallic silicides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
- H01L21/02485—Other chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
- H01L21/02491—Conductive materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
- H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero- junctions, X being an element of Group VI of the Periodic Table
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- H—ELECTRICITY
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention is in the technical field of producing thin-film solar cells and relates to a layer system for thin-film solar cells and a method for producing such a layer system.
- Photovoltaic layer systems for solar cells for the direct conversion of sunlight into electrical energy are well known.
- the term "thin-film solar cells” refers to layer systems with a thickness of only a few micrometers that require (carrier) substrates for sufficient mechanical strength.
- Known substrates include inorganic glass, plastics (polymers) or metals, in particular metal alloys, and can be designed as rigid plates or flexible foils depending on the respective layer thickness and the specific material properties.
- Layer systems for thin-film solar cells are available on the market in various designs, depending on the substrate and the materials applied. The materials are selected in such a way that the incident solar spectrum is used to the maximum. Due to the physical properties and technological manageability, layer systems with amorphous, micromorphous or polycrystalline silicon, cadmium telluride (CdTe), gallium arsenide (GaAs), copper indium (gallium) selenide sulfide (Cu(In,Ga) (S,Se) 2 ), copper-zinc-tin-sulfo-selenide (CZTS from the kesterite group) and organic semiconductors, particularly suitable for thin-film solar cells.
- CdTe cadmium telluride
- GaAs gallium arsenide
- Cu(In,Ga) (S,Se) 2 copper-zinc-tin-sulfo-selenide
- organic semiconductors particularly suitable for thin-film solar cells.
- the pentenary semiconductor Cu(In,Ga) (S,Se) 2 belongs to the group of chalcopyrite semiconductors, often referred to as CIS (copper indium diselenide or -sulfide) or CIGS (copper indium gallium diselenide, copper indium gallium disulphide or copper indium gallium disulfoselenide).
- CIS copper indium diselenide or -sulfide
- CIGS copper indium gallium diselenide, copper indium gallium disulphide or copper indium gallium disulfoselenide.
- S in the abbreviation CIGS can stand for selenium, sulfur or a mixture of both chalcogens.
- CdS cadmium sulfide
- CBD process chemical bath process
- CdS buffer layer contains the toxic heavy metal cadmium. This results in higher production costs, since increased safety precautions have to be taken in the production process, for example when disposing of the waste water. Disposing of the product may result in additional costs for the customer as the manufacturer may be required to take back, dispose of or recycle the product depending on local legislation.
- these materials are not yet suitable as buffers for solar cells based on Cu(In,Ga)(S,Se) 2 for commercial use, since they do not achieve the same efficiencies as those with a CdS buffer layer.
- the efficiency describes the ratio of radiated power to the electrical power generated by a solar cell and is up to about 20% for CdS buffer layers for laboratory cells on small areas and between 10% and 15% for large-area modules.
- alternative buffer layers exhibit excessive instabilities, hysteresis effects or degradations in efficiency when exposed to light, heat and/or humidity.
- CdS buffer layers Another disadvantage of CdS buffer layers is that cadmium sulfide is a direct semiconductor with a direct electronic band gap of about 2.4 eV. Therefore, in a Cu(In,Ga)(S,Se) 2 /CdS/ZnO solar cell, the incident light is absorbed to a considerable extent even with a CdS layer thickness of a few 10 nm. The light absorbed in the buffer layer is lost for the electrical yield, since the generated charge carriers recombine again immediately in this layer and there are many crystal defects acting as recombination centers in this region of the heterojunction and in the buffer material. As a result, the efficiency of the solar cell decreases, which is disadvantageous for a thin-film solar cell.
- a layer system with a buffer layer based on indium sulfide is possible WO 2009/141132 A2 famous.
- the layer system consists of a chalcopyrite absorber of the CIGS family and in particular of Cu(In,Ga)(S,Se) 2 in connection with a buffer layer of indium sulfide.
- the indium sulfide buffer layer can be deposited using various non-wet chemical methods, for example thermal evaporation, electron beam evaporation, ion layer gas reaction (ILGAR), sputtering (sputtering), atomic layer deposition (ALD) or spray pyrolysis.
- ILGAR ion layer gas reaction
- sputtering sputtering
- ALD atomic layer deposition
- a buffer layer based on sodium-alloyed indium sulfide is made Barreau et al.: "Study of the new ⁇ -In2S3 containing Na thin films. Part II: Optical and electrical characterization of thin films", Journal of Crystal Growth, 241 (2002), pp. 51-56 , famous.
- the object of the present invention is to provide a layer system based on a chalcopyrite compound semiconductor with a buffer layer, which has a high efficiency and high stability, the production should be inexpensive and environmentally friendly. According to the proposal of the invention, these and other objects are achieved by a layer system and a method for producing a layer system with the features of the independent patent claims. Advantageous configurations of the invention are specified by the features of the dependent claims.
- the layer system according to the invention for thin-layer solar cells comprises an absorber layer for absorbing light.
- the absorber layer contains a chalcopyrite compound semiconductor, in particular Cu 2 ZnSn(S,Se) 4 , Cu(In,Ga,Al)(S,Se) 2 , CuInSe 2 , CuInS 2 , Cu(In,Ga) Se2 or Cu(In,Ga)(S,Se )2 .
- the absorber layer it consists of such a chalcopyrite compound semiconductor.
- the layer system according to the invention comprises a buffer layer arranged on the absorber layer, which contains sodium indium sulfide according to the empirical formula Na x In yx/3 S with 0.063 ⁇ x ⁇ 0.625 and 0.681 ⁇ y ⁇ 1.50.
- the molecular formula Na x In yx/3 S describes the mole fractions of sodium, indium and sulfur in the buffer layer, based on sodium indium sulfide, where the index x represents the mole amount of sodium and the index x and a further index y are decisive for the mole amount of indium where the amount of substance of indium results from the value of yx/3.
- the index is always 1.
- the mole fraction of a substance (element) of sodium indium sulfide in atomic % describes the fraction of the mole fraction of this substance (element) in sodium indium sulfide based on the sum of the moles of all substances (elements) of the molecular formula.
- the mole fraction of a substance related to sodium indium sulfide corresponds to the mole fraction of the substance in the buffer layer if there are no other elements than sodium, indium and sulfur in the buffer layer or if these elements have a negligible proportion.
- the buffer layer is composed (or consists) of sodium indium sulfide according to the empirical formula Na x In yx/3 S with 0.063 ⁇ x ⁇ 0.625 and 0.681 ⁇ y ⁇ 1.50 and one or more other components (impurities) different from this.
- the buffer layer essentially consists of sodium indium sulfide according to the empirical formula Na x In yx/3 S with 0.063 ⁇ x ⁇ 0.625 and 0.681 ⁇ y ⁇ 1.50. This means that the other components (impurities) have a negligible proportion.
- the mole fraction of a substance (impurity) in atomic % describes the proportion of the mole fraction of this substance in relation to the sum of the moles of all substances in the buffer layer (i.e. based on sodium indium sulfide and impurities).
- the percentage (atomic %) of all elements of sodium indium sulfide according to the empirical formula Na x In yx / 3 S with 0.063 ⁇ x ⁇ 0.625 and 0.681 ⁇ y ⁇ 1.50 in the buffer layer is at least 75%, preferably at least 80%, more preferably at least 85%, even more preferably at least 90%, even more preferably at least 95% and most preferably at least 99%.
- the elements of the buffer layer can each be present in different oxidation states, all oxidation states are uniformly referred to below with the name of the element, unless this is explicitly indicated otherwise.
- sodium is therefore to be understood as meaning elementary sodium, sodium ions and sodium in compounds.
- the sodium indium sulfide buffer layer of the layer system according to the invention advantageously has an amorphous or finely crystalline structure.
- the average grain size is limited by the thickness of the buffer layer and is advantageously in the range from 8 nm to 100 nm and more preferably in the range from 20 nm to 60 nm, for example 30 nm.
- the amorphous or finely crystalline structure can prevent copper (Cu) from diffusing from the absorber layer into the buffer layer.
- Cu copper
- the indiffusion of larger amounts of copper is disadvantageous, since the band gap of the buffer layer is reduced by copper. This leads to increased absorption of the light in the buffer layer and thus to a reduction in efficiency.
- a particularly high degree of efficiency of the solar cell can be ensured by a mole fraction of copper in the buffer layer of less than 7 atom %, in particular less than 5 atom %.
- the buffer layer contains sodium indium sulfide according to the molecular formula Na x In yx/3 S with 0.063 ⁇ x ⁇ 0.469 and 0.681 ⁇ y ⁇ 1.01. For these values could particularly high efficiencies are measured. The best efficiencies to date have been measured for a buffer layer containing sodium indium sulfide according to the molecular formula Na x In yx/3 S with 0.13 ⁇ x ⁇ 0.32 and 0.681 ⁇ y ⁇ 0.78.
- the buffer layer has a mole fraction of sodium of more than 5 atom %, in particular more than 7 atom %, in particular more than 7.2 atom %. Particularly high efficiencies were measured for such a high proportion of sodium. Furthermore, for a buffer layer according to the invention, the ratio of the mole fractions of sodium and indium is greater than 0.2.
- the buffer layer contains a mole fraction of a halogen, in particular chlorine, of less than 7 atom %, in particular less than 5 atom %, it being preferred if the buffer layer is completely halogen-free.
- a halogen in particular chlorine
- the buffer layer has a mole fraction of copper of less than 7 atom %, in particular less than 5 atom %, it being preferred if the buffer layer is completely copper-free.
- the buffer layer according to the invention contains a mole fraction of oxygen of at most 10 atom %.
- Oxygen can occur as an impurity, since indium sulfide, for example, is hygroscopic. Oxygen can also be carried in via residual water vapor from the coating systems. A particularly high degree of efficiency of the solar cell can be ensured by a mole fraction of ⁇ 10 atomic % of oxygen in the buffer layer.
- the buffer layer does not contain any significant proportion of other elements apart from sodium, indium and sulphur, Cl and O. This means that the buffer layer is not provided with other elements, such as carbon, for example, and at most contains ⁇ 1 atom % of other elements that are unavoidable in terms of production technology. This ensures a high degree of efficiency of the solar cell.
- the sum of the mole fractions of all impurities is in of the buffer layer at most 25%, preferably at most 20%, more preferably at most 15%, even more preferably at most 10%, even more preferably at most 5% and most preferably at most 1%.
- the buffer layer consists of a first layer area adjoining the absorber layer and a second layer area adjoining the first layer area, the layer thickness of the first layer area being smaller than the layer thickness of the second layer area or equal to the layer thickness of the second layer area, and wherein the mole fraction of sodium has a maximum in the first layer region and decreases towards both the absorber layer and the second layer region.
- An advantageous embodiment of the buffer layer according to the invention has a layer thickness of 10 nm to 100 nm and preferably of 20 nm to 60 nm.
- the invention also extends to thin-film solar cells with the layer system according to the invention and solar cell modules that contain these solar cells.
- a thin-film solar cell according to the invention comprises a substrate, a rear electrode arranged on the substrate, a layer system according to the invention arranged on the rear electrode, and a front electrode arranged on the second buffer layer.
- the substrate is preferably a metal, glass, plastic or ceramic substrate, with glass being preferred. However, other transparent carrier materials, in particular plastics, can also be used.
- the back electrode advantageously comprises molybdenum (Mo) or other metals. In an advantageous configuration of the rear electrode, it has a molybdenum sub-layer that adjoins the absorber layer and a silicon nitride sub-layer (SiN) that adjoins the molybdenum sub-layer.
- Such rear electrode systems are made, for example EP 1356528 A1 famous.
- the front electrode preferably contains a transparent conductive oxide (TCO), particularly preferably aluminum, gallium or boron-doped zinc oxide and/or indium tin oxide (ITO).
- the layer system according to the invention produced in the method according to the invention is designed as described in connection with the layer system according to the invention.
- the absorber layer is expediently applied to the back electrode on a substrate in an RTP (“rapid thermal processing”) process.
- a precursor layer is first deposited on the substrate with the back electrode.
- the precursor layer contains the elements copper, indium and gallium, which are applied by sputtering.
- a targeted dose of sodium is introduced into the precursor layer, such as from EP 715 358 B1 is known.
- the precursor layer contains elemental selenium, which is applied by thermal evaporation.
- the substrate temperature is below 100°C, so that the elements essentially remain unreacted as metal alloys and elementary selenium.
- This precursor layer is then reacted in a rapid annealing process (rapid thermal processing, RTP) in a sulfur-containing atmosphere to form a Cu(In,Ga)(S,Se) 2 -chalcogenide semiconductor.
- RTP rapid thermal processing
- indium sulfide preferably In 2 S 3
- a sodium sulfide preferably Na 2 S, in particular a sodium polysulfide, before and/or during and/or after the deposition of indium sulfide , preferably Na 2 S 3 or Na 2 S 4 , or a sodium indate, preferably NaInS 2 or NaIn 5 S 8 , deposited on the absorber layer.
- sodium sulfide or sodium indate is deposited alternately with indium sulfide, for example starting with sodium sulfide or sodium indate.
- the buffer layer according to the invention is advantageously formed by wet chemical bath deposition, atomic layer deposition (ALD), ion layer gas deposition (ILGAR), spray pyrolysis, chemical vapor deposition (CVD) or physical vapor Deposition (PVD) applied to the absorber layer.
- the buffer layer according to the invention is preferably deposited by sputtering (cathode sputtering), thermal evaporation or electron beam evaporation, particularly preferably from separate sources for indium sulphide and sodium sulphide or sodium indate.
- Indium sulfide can be evaporated either from separate sources for indium and sulfur or from a source with an In 2 S 3 compound semiconductor material. Other indium sulfides (In 6 S 7 or InS) are also possible in combination with a sulfur source.
- the buffer layer according to the invention is advantageously deposited using a vacuum method.
- the vacuum process has the particular advantage that the incorporation of oxygen or hydroxide is prevented in the vacuum. Hydroxide components in the buffer layer are believed to be responsible for efficiency transients upon exposure to heat and light. Furthermore, vacuum processes have the advantage that the process does not require wet chemicals and standard vacuum coating systems can be used.
- sodium sulphide preferably Na 2 S
- sodium indate is evaporated from at least one separate, second source.
- the deposition sources can be arranged in such a way that the vapor lobes of the sources do not overlap.
- the arrangement of the deposition sources can be designed in such a way that the vapor lobes of the sources completely or partially overlap.
- vapor lobe means the area in front of the outlet of the source which is technically suitable for the deposition of the vaporized material on a substrate in terms of vaporization rate and homogeneity.
- the source is, for example, an effusion cell, a boat or crucible of a thermal evaporator, a resistance heater, an electron beam evaporator or a linear evaporator.
- the absorber layer is guided past at least one vapor lobe of sodium sulfide or sodium indate and at least one vapor lobe of indium sulfide or indium and sulfur in an in-line process or in a rotation process.
- the absorber layer can be guided past a vapor lobe of sodium sulfide or sodium indate and then a vapor lobe of indium sulfide. It is also possible, for example, for the absorber layer to be guided past a vapor lobe of sodium sulfide or sodium indate, which is located between two vapor lobes of indium sulfide.
- Another aspect of the invention includes the use of a layer system according to the invention in a thin-film solar cell or a solar cell module.
- FIG. 1 shows a preferred exemplary embodiment of a thin-film solar cell 100 according to the invention in a purely schematic manner with a layer system 1 according to the invention in a cross-sectional view.
- the thin-film solar cell 100 contains a substrate 2 and a back electrode 3.
- a layer system 1 according to the invention is arranged on the back electrode 3.
- FIG. The layer system 1 according to the invention comprises an absorber layer 4 and a buffer layer 5.
- a second buffer layer 6 and a front electrode 7 are arranged on the layer system 1.
- the substrate 2 consists here, for example, of inorganic glass, with other insulating materials with sufficient strength and inert behavior towards the process steps carried out in the production of the thin-film solar cell 100 being able to be used, for example plastics, in particular polymers or metals, in particular metal alloys.
- the substrate 2 can be designed as a rigid plate or flexible film.
- the layer thickness of the substrate 2 is, for example, from 1 mm to 5 mm.
- a back electrode 3 is arranged on the surface of the substrate 2 on the light entry side.
- the back electrode 3 consists, for example, of an opaque metal. It can be deposited on the substrate 2, for example, by vapor deposition or by cathode sputtering supported by a magnetic field.
- the back electrode 3 consists, for example, of molybdenum (Mo), aluminum (Al), copper (Cu), titanium (Ti), zinc (Zn) or of a multi-layer system with such a metal, for example molybdenum (Mo).
- the layer thickness of the rear electrode 3 is less than 1 ⁇ m here, is preferably in the range from 300 nm to 600 nm and is, for example, 500 nm.
- the rear electrode 3 serves as a rear contact of the thin-film solar cell 100.
- An alkaline be arranged barrier, which for example made of Si 3 N 4 , SiON or SiCN. this is in figure 1 not shown in detail.
- a layer system 1 according to the invention is arranged on the rear electrode 3 .
- the layer system 1 contains an absorber layer 4 , for example made of Cu(In,Ga)(S,Se) 2 , which is applied directly to the back electrode 3 .
- the absorber layer 4 made of Cu(InGa)(S,Se) 2 was deposited, for example, in the RTP process described above.
- the absorber layer 4 has a thickness of 1.5 ⁇ m, for example.
- a buffer layer 5 is arranged on the absorber layer 4 .
- the buffer layer 5 contains Na x In yx/3S with 0.063 ⁇ x ⁇ 0.625, 0.681 ⁇ y ⁇ 1.50, preferably 0.063 ⁇ x ⁇ 0.469, 0.681 ⁇ y ⁇ 1.01, and more preferably 0.13 ⁇ x ⁇ 0.32, 0.681 ⁇ y ⁇ 0.78.
- the layer thickness of the buffer layer 5 is in the range from 20 nm to 60 nm and is 30 nm, for example.
- a second buffer layer 6 can optionally be arranged above the buffer layer 5 .
- the buffer layer 6 contains, for example, undoped zinc oxide (i-ZnO).
- a front electrode 7 is arranged above the second buffer layer 6, which serves as a front-side contact and is transparent to radiation in the visible spectral range ("window layer").
- the layer thickness of the front electrode 7 is, for example, about 300 to 1500 nm.
- a plastic layer made, for example, of polyvinyl butyral (PVB), ethylene vinyl acetate (EVA) or silicone can be applied to the front electrode 7 .
- a cover plate that is transparent to sunlight can be provided, for example made of extra-white glass (front glass) with a low iron content and has a thickness of, for example, 1 to 4 mm.
- the substrate configuration shown is adjacent to the rear electrode 3 to the substrate 2. It goes without saying that the layer system 1 can equally have a superstrate configuration in which the substrate 2 is transparent and the front electrode 7 is arranged on a surface of the substrate 2 which is remote from the light entry side.
- the layer system 1 can be used to produce integrated series-connected thin-film solar cells 100, the layer system 1, the rear electrode 3 and the front electrode 7 being defined in a manner known per se by various structuring lines (“P1” for rear electrode, “P2” for contact front electrode/rear electrode and “ P3” for separation of the front electrode) is structured.
- P1 for rear electrode
- P2 for contact front electrode/rear electrode
- P3 for separation of the front electrode
- FIG. 2A 12 is a ternary diagram showing the composition Na x In yx/3S of the buffer layer 5 of the thin film solar cell 100 of FIG 1 shown.
- the relative proportions of the components sulfur (S), indium (In) and sodium (Na) of the buffer layer 5 are indicated in the ternary diagram.
- the composition range claimed according to the invention given by 0.063 ⁇ x ⁇ 0.625 and 0.681 ⁇ y ⁇ 1.50, is given by the area enclosed by a solid line. Data points within the boxed composition range indicate exemplary compositions of the buffer layer 5.
- FIG. Figure 2B shows an enlarged section of the ternary diagram with the according to the invention claimed compositional range.
- these buffer layers have a band gap of 2.95 eV with a sodium content of more than 6 atom %, which results in an unfavorable band matching to the absorber or to the front electrode and thus leads to a deterioration in the electrical properties. so that these buffer layers are unsuitable for use in thin-film solar cells. According to Barreau et al. inaccessible.
- a relatively low sulfur content in the buffer layer 5 enables a higher sodium content, with the layer properties favorable for band matching in the solar cells being retained.
- the composition can be controlled in a targeted manner in an indium-enriched range.
- the band gap and the charge carrier concentration of the buffer layer 5 can be set by alloying with sodium, as a result of which the electronic transition from the absorber layer 4 via the buffer layer 5 to the front electrode 7 can be optimized. This is explained in more detail below.
- Figure 3A shows a diagram in which the efficiency Eta (percent) of the thin film solar cell 100 of figure 1 is plotted against the sodium-indium content in the buffer layer 5. This is a corresponding projection Figure 2A .
- Figure 3B shows a diagram in which the efficiency Eta (percent) of the thin film solar cell 100 of figure 1 is plotted against the absolute sodium content (atomic %) in the buffer layer 5 .
- the thin-film solar cell 100 used for this purpose contains a substrate 2 made of glass and a back electrode 3 made of an Si 3 N 4 barrier layer and a molybdenum layer.
- An absorber layer 4 made of Cu(In,Ga)(S,Se) 2 is arranged on the rear electrode 3 and was deposited according to the RTP process described above.
- An Na x In yx/3 S buffer layer 5 with 0.063 ⁇ x ⁇ 0.625 and 0.681 ⁇ y ⁇ 1.50 is arranged on the absorber layer 4 .
- the layer thickness of the buffer layer 5 is 50 nm.
- a 100 nm thick second buffer layer 6 containing undoped zinc oxide is arranged on the buffer layer 5 .
- a 1200 nm thick front electrode 7 containing n-conducting zinc oxide is arranged on the second buffer layer 6 .
- the area of the thin-film solar cell 100 is 1.4 cm 2 , for example.
- the buffer layer 5 according to the invention can thus achieve a significant improvement in the efficiency of the thin-film solar cell 100 without a deterioration in the electrical layer properties (good band matching to the absorber or front electrode due to a band gap that is not too large).
- figure 5 shows a depth profile of the sodium distribution in the buffer layer 5 of the layer system 1 of FIG 1 .
- the normalized depth is plotted as the abscissa and the normalized signal intensity is plotted as the ordinate.
- the range from 0 to 1 on the abscissa marks the buffer layer 5 and the range with values greater than 1 the absorber layer 4.
- Compounds of sodium with the chalcogen sulfur (S), preferably Na 2 S were used as the starting materials for the sodium alloy of the indium sulfide layer. It would also be equally conceivable to use a compound of sodium with sulfur and indium, for example NaIn 3 S 5 .
- the buffer layer 5, which is respectively applied to a CIGSSe absorber layer 4, contains different amounts of sodium (Quantity 1, Quantity 2). An indium sulfide buffer layer not alloyed with sodium was used as a reference.
- the sodium alloy causes an increase in the sodium content in the layer stack, with a slight enrichment of the sodium content in the buffer layer 5 ("doping peak") occurring despite uniform deposition of the alloy at the absorber-buffer interface due to diffusion mechanisms.
- the buffer layer 5 can be divided at least conceptually into two areas, namely a first layer area adjoining the absorber layer and a second layer area adjoining the first layer area, the layer thickness of the first layer area being equal to the layer thickness of the second layer area, for example. Accordingly, the mole fraction of sodium has a maximum in the first layer region and decreases both towards the absorber layer 4 and towards the second layer region. A specific sodium concentration is maintained in the buffer layer 5 over the entire layer thickness. The accumulation of sodium at the absorber-buffer interface is probably due to a high defect density at this point.
- oxygen (O) or zinc (Zn) can also accumulate in the buffer layer 5, for example through diffusion from the TCO of the front electrode 7. Due to the hygroscopic properties of the starting materials, an enrichment of water from the ambient air is also conceivable.
- the proportion of halogen in the buffer layer according to the invention is particularly advantageously low, with the proportion of a halogen, for example chlorine, being less than 5 atom %, in particular less than 1 atom %.
- the buffer layer 5 is particularly advantageously halogen-free.
- FIG 6 shows a flow chart of a method according to the invention.
- an absorber layer 4 is made, for example, from a Cu(In,Ga)(S,Se) 2 semiconductor material provided.
- the buffer layer 5 made of sodium indium sulfide is deposited.
- the ratio of the individual components in the buffer layer 5 is regulated, for example, by controlling the evaporation rate, for example by means of an aperture or a temperature control.
- a second buffer layer 6 and a front electrode 7 can be deposited on the buffer layer 5 in further process steps.
- the layer structure 1 can be connected and contacted to form a thin-film solar cell 100 or a solar module.
- FIG 7 shows a schematic representation of an in-line method for producing a buffer layer 5 made of sodium indium sulfide according to the invention.
- the substrate 2 with rear electrode 3 and absorber layer 4 is in an in-line process on the vapor lobes 11,12 of, for example, an indium sulfide source 8, preferably In 2 S 3 , a sodium sulfide source 9, preferably Na 2 S, and a second indium sulfide source 8, preferably In 2 S 3 , passed.
- the direction of transport is indicated by an arrow with reference number 10 .
- the sodium sulfide source 9 is arranged in the transport direction 10 between the two indium sulfide sources 8, with the vapor lobes 11, 12 not overlapping.
- the absorber layer 4 is coated first with a thin layer of indium sulfide, then with a thin layer of sodium sulfide, and then again with a thin layer of indium sulfide, which mix.
- the sodium sulfide source 9 and the indium sulfide sources 8 are, for example, effusion cells from which sodium sulfide or indium sulfide is thermally evaporated.
- the non-overlapping sources enable a particularly simple process control. It would be conceivable to arrange any number of sodium sulfide sources 9 and any number of indium sulfide sources 8 with non-overlapping sources in the transport direction 10, preferably alternating, preferably starting with a sodium sulfide source 9.
- any other form of generating vapor lobes 11, 12 is suitable for depositing the buffer layer 5, provided that the ratio of the mole fractions of sodium, indium and sulfur can be controlled.
- Alternative sources are, for example, boats from linear evaporators or crucibles from electron beam evaporators.
- FIG 8 an alternative device for carrying out the method according to the invention is shown, only the differences to the device of FIG figure 7 are explained and otherwise reference is made to the above statements.
- the substrate 2 is guided past the vapor lobes 11,12 of two sodium sulfide (Na 2 S) sources 9 and two indium sulfide (In 2 S 3 ) sources 8 in an in-line process, which alternate in the transport direction 10 (Na 2 S - In 2 S 3 - Na 2 S - In 2 S 3 ) are arranged (starting with a sodium sulfide source), the vapor lobes 11, 12 partially overlapping here, for example. It would also be conceivable that the steam lobes completely overlap.
- Na 2 S sodium sulfide
- In 2 S 3 indium sulfide
- Sodium sulfide is thus applied before and also during the application of indium sulfide, as a result of which particularly good mixing of sodium sulfide and indium sulfide can be achieved. It would be conceivable to arrange any number of sodium sulfide sources 9 and any number of indium sulfide sources 8 with partially or completely overlapping sources in the transport direction 10, preferably alternating, preferably starting with a sodium sulfide source 9.
- FIG 9 shows a further alternative embodiment of the method according to the invention using the example of a rotation method.
- the substrate 2 with the back electrode 3 and the absorber layer 4 is arranged on a rotatable sample carrier 13, for example on a sample carousel.
- Below the sample carrier 13 are alternately arranged sources of sodium sulfide 9 and indium sulfide 8.
- the Sample carrier 13 rotated. As a result, the substrate 2 is moved and coated in the vapor lobes 11,12.
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Claims (13)
- Système de couches (1) pour les cellules solaires à couche mince (100), comprenant :- une couche absorbante (4) pour l'absorption de la lumière,- une couche tampon (5) disposée sur ladite couche absorbante (4), contenant NaxIny-x/3S, dans laquelle :caractérisé en ce que, le pourcentage de tous les éléments de NaxIny-x/3S dans ladite couche tampon (5) est d'au moins 75 Atome-%;0,063 ≤ x ≤ 0,625,0,681 ≤ y ≤ 1,50
dans ladite couche tampon (5), le rapport des fractions molaires de sodium et d'indium est supérieur à 0,2. - Système de couches (1) selon la revendication 1, caractérisé en ce que ladite couche tampon (5) contient NaxIny-x/3S, dans laquelle :0,063 ≤ x ≤ 0,469,0,681 ≤ y ≤ 1,01.
- Système de couches (1) selon la revendication 1, caractérisé en ce que ladite couche tampon (5) contient NaxIny-x/3S, dans laquelle :0,13 ≤ x ≤ 0,32,0,681 ≤ y ≤ 0,78.
- Système de couches (1) selon l'une quelconque des revendications 1 à 3, caractérisé en ce que ladite couche tampon (5) présente une fraction molaire de sodium supérieure à 5 Atome-%.
- Système de couches (1) selon l'une quelconque des revendications 1 à 4, caractérisé en ce que ladite couche tampon (5) contient une fraction molaire d'halogène ou de cuivre inférieure à 7 Atome-%.
- Système de couches (1) selon l'une quelconque des revendications 1 à 5, caractérisé en ce que ladite couche tampon (5) contient une fraction molaire d'oxygène inférieure à 10 Atome-%.
- Système de couches (1) selon l'une quelconque des revendications 1 à 6, caractérisé en ce que ladite couche tampon (5) présente une épaisseur de couche de 10 nm à 100 nm, ladite couche tampon (5) étant amorphe ou finement cristalline.
- Système de couches (1) selon l'une quelconque des revendications 1 à 7, caractérisé en ce que ladite couche absorbante (4) contient un semi-conducteur composé de chalcopyrite.
- Cellule solaire à couche mince (100), comprenant :- un substrat (2),- une électrode arrière (3) disposée sur ledit substrat (2),- un système de couches (1) selon l'une quelconque des revendications 1 à 8, qui est disposé sur ledit électrode arrière (3), et- une électrode avant (7) disposée sur ledit système de couches (1).
- Procédé de fabrication d'un système de couches (1) pour les cellules solaires à couche mince (100) selon l'une quelconque des revendications 1 à 8, caractérisé en ce que,a) une couche absorbante (4) est fabriquée,b) une couche tampon (5) est fabriquée sur ladite couche absorbante (4), la couche tampon (5) contenant NaxIny-x/3S, dans laquelle :caractérisé en ce que le pourcentage de tous les éléments de NaxIny-x/3S dans ladite couche tampon (5) est d'au moins 75 Atome-%.0,063 ≤ x ≤ 0,625,0,681 ≤ y ≤ 1,50
- Procédé selon la revendication 10, caractérisé en ce que, pour la fabrication de ladite couche tampon (5) à l'étape b) :- du sulfure d'indium est déposé sur ladite couche absorbante (4), et- avant et/ou pendant et/ou après le dépôt du sulfure d'indium, du sulfure de sodium ou de l'indate de sodium est déposé sur ladite couche absorbante (4).
- Procédé selon la revendication 10 ou 11, caractérisé en ce que, ledit sulfure de sodium ou ledit indate de sodium est déposé par dépôt en bain chimique par voie humide, dépôt par couche atomique (ALD), dépôt par couche ionique en phase gazeuse (ILGAR), pyrolyse par pulvérisation, dépôt chimique en phase vapeur (CVD) ou dépôt physique en phase vapeur (PVD), pulvérisation, évaporation thermique ou évaporation par faisceau d'électrons.
- Procédé selon l'une quelconque des revendications 10 à 12, caractérisé en ce que, ladite couche absorbante (4) passe devant au moins un faisceau de vapeur (12) de sulfure de sodium ou d'indate de sodium, et au moins un faisceau de vapeur (11) de sulfure d'indium dans un procédé en ligne ou dans un procédé de rotation.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13173956 | 2013-06-27 | ||
PCT/EP2014/063747 WO2014207226A1 (fr) | 2013-06-27 | 2014-06-27 | Système de couches pour cellules solaires à couches minces, présentant une couche tampon renfermant du sulfure d'indium sodique |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3014652A1 EP3014652A1 (fr) | 2016-05-04 |
EP3014652B1 true EP3014652B1 (fr) | 2022-02-16 |
Family
ID=48692333
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14734459.2A Active EP3014652B1 (fr) | 2013-06-27 | 2014-06-27 | Système de couches pour cellules solaires à couches minces avec couche-tampon en sulfure de sodium |
Country Status (7)
Country | Link |
---|---|
US (1) | US20160163905A1 (fr) |
EP (1) | EP3014652B1 (fr) |
JP (1) | JP6147926B2 (fr) |
KR (1) | KR101799087B1 (fr) |
CN (1) | CN105474371B (fr) |
ES (1) | ES2909538T3 (fr) |
WO (1) | WO2014207226A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180103676A (ko) * | 2014-12-22 | 2018-09-19 | 벵부 디자인 앤드 리서치 인스티튜트 포 글래스 인더스트리 | 나트륨 인듐 술피드 버퍼 층을 갖는 박층 태양 전지용 층 시스템의 제조 방법 |
EP3627564A1 (fr) | 2018-09-22 | 2020-03-25 | (CNBM) Bengbu Design & Research Institute for Glass Industry Co., Ltd. | Procédé de traitement ultérieur d'une couche absorbante |
KR102686362B1 (ko) | 2018-10-12 | 2024-07-22 | 삼성디스플레이 주식회사 | 증착 장치 및 이를 이용한 표시 장치 제조 방법 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4442824C1 (de) | 1994-12-01 | 1996-01-25 | Siemens Ag | Solarzelle mit Chalkopyrit-Absorberschicht |
JPH10125941A (ja) * | 1996-10-23 | 1998-05-15 | Asahi Chem Ind Co Ltd | カルコパイライト型太陽電池 |
JPH11204810A (ja) * | 1998-01-08 | 1999-07-30 | Asahi Chem Ind Co Ltd | 化合物半導体太陽電池 |
JP2000174306A (ja) * | 1998-12-01 | 2000-06-23 | Asahi Chem Ind Co Ltd | 化合物半導体薄膜の製造方法 |
DE19956735B4 (de) | 1999-11-25 | 2008-08-21 | Shell Erneuerbare Energien Gmbh | Dünnfilmsolarzelle mit einer Chalkopyritverbindung und einer Titan und Sauerstoff enthaltenden Verbindung |
FR2820241B1 (fr) | 2001-01-31 | 2003-09-19 | Saint Gobain | Substrat transparent muni d'une electrode |
FR2826951B1 (fr) * | 2001-07-06 | 2003-09-26 | Univ Nantes | Nouveau compose derive de la variete spinelle de sulfure d'indium, ses procedes de fabrication et ses applications |
EP3327170B1 (fr) * | 2007-09-12 | 2020-11-04 | Flisom AG | Appareil pour fabriquer un film d'un composé |
DE102008024230A1 (de) | 2008-05-19 | 2009-11-26 | Avancis Gmbh & Co. Kg | Schichtsystem für Solarzellen |
EP2360289A1 (fr) | 2010-02-23 | 2011-08-24 | Saint-Gobain Glass France | Dispositif et procédé de dépot d'une couche composée d'au moins deux composants sur un substrat |
WO2011109228A1 (fr) * | 2010-03-05 | 2011-09-09 | First Solar, Inc. | Dispositif photovoltaïque doté d'une couche tampon étagée |
-
2014
- 2014-06-27 WO PCT/EP2014/063747 patent/WO2014207226A1/fr active Application Filing
- 2014-06-27 EP EP14734459.2A patent/EP3014652B1/fr active Active
- 2014-06-27 ES ES14734459T patent/ES2909538T3/es active Active
- 2014-06-27 CN CN201480047433.0A patent/CN105474371B/zh active Active
- 2014-06-27 US US14/900,939 patent/US20160163905A1/en not_active Abandoned
- 2014-06-27 KR KR1020167001898A patent/KR101799087B1/ko active IP Right Grant
- 2014-06-27 JP JP2016522545A patent/JP6147926B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
JP6147926B2 (ja) | 2017-06-14 |
KR101799087B1 (ko) | 2017-11-20 |
CN105474371A (zh) | 2016-04-06 |
KR20160023842A (ko) | 2016-03-03 |
ES2909538T3 (es) | 2022-05-06 |
CN105474371B (zh) | 2018-03-27 |
US20160163905A1 (en) | 2016-06-09 |
JP2016524340A (ja) | 2016-08-12 |
WO2014207226A1 (fr) | 2014-12-31 |
EP3014652A1 (fr) | 2016-05-04 |
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